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Kinetic Analysis of Nitroxide Radical Formation Under Oxygenated Photolysis: Toward Quantitative Singlet Oxygen Topology

22-10-2014 | Malcolm Forbes; David F Zigler; Eva Chuheng Ding; Renat Khatmullin; Vanessa M DiPasquale; Valery F Tarasov; R. Brend ..., Photochemical & Photobiological Sciences, 2014

Reaction kinetics for two sterically hindered secondary amines with singlet oxygen have been studied in detail. A water soluble porphyrin sensitizer, 5,10,15,20-tetrakis-(4-sulfunatophenyl)-21,23H-porphyrin (TPPS), was irradiated in oxygenated aqueous solutions containing either ...

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Theoretical Investigation of Thermodynamic Stability and Mobility of the Oxygen Vacancy in ThO2-UO2 Solid Solutions

21-10-2014 | Bin Liu; Dilpuneet Aidhy; Yanwen Zhang; William J. Weber, Physical Chemistry Chemical Physics, 2014

The thermodynamic stability and the migration energy barriers of oxygen vacancies in ThO2-UO2 solid solutions are investigated by density functional theory calculations. In pure ThO2, the formation energy of oxygen vacancy is 7.58 eV and 1.46 eV under O rich and O poor conditions, respectively, ...

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Synthesis and Conformational Studies of a Peptidomimetic [small beta]-Hairpin Mimic as a Potential [small beta]-Sheet Binder

21-10-2014 | Umberto Piarulli; Leila Vahdati; Roberto Fanelli; Isabelle Correia; Olivier Lequin; Sandrine Ongeri; Guillaume Bernadat, New Journal of Chemistry, 2014

The design, synthesis and conformational studies of a new β-hairpin mimic, 2, are described in this paper. The design towards hairpin 2 is based on the assembly of the bifunctional DKP-1 as a β-turn inducer, a peptidomimetic strand, namely 5-amino-2-methoxybenzhydrazide, to stabilize the ...

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Recent advances in C–S bond formation via C–H bond functionalization and decarboxylation

21-10-2014 | Chao Shen; Pengfei Zhang; Qiang Sun; Shiqiang Bai; T. S. Andy Hor; Xiaogang Liu, Chemical Society Reviews, 2014

The development of mild and general methods for C–S bond formation has received significant attention because the C–S bond is indispensable in many important biological and pharmaceutical compounds. Early examples for the synthesis of C–S bonds are generally limited to the condensation reaction ...

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One-step propylene formation from bio-glycerol over molybdena-based catalysts

21-10-2014 | Vasiliki Zacharopoulou; Efterpi S. Vasiliadou; Angeliki A. Lemonidou, Green Chemistry, 2014

This work presents a novel, one-step catalytic process, enabling highly selective propylene formation via glycerol hydro-deoxygenation (HDO) reactions. Fe–Mo catalysts, supported on black and activated carbons, are selective towards C–O bond cleavage, thus converting glycerol to propylene with ...

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Highly efficient green-light ionization of an aryl radical anion: key step in a catalytic cycle of electron formation

21-10-2014 | Christoph Kerzig; Martin Goez, Physical Chemistry Chemical Physics, 2014

A sustainable generation of hydrated electrons with green light would allow solar-driven applications of this potent reductant, such as the detoxification of halogenated organic waste. Using two-color laser flash photolysis, we have studied the photoionizations of the 1,5-naphthalene disulfonate ...

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Catalytic methylation of aromatic amines with formic acid as the unique carbon and hydrogen source

21-10-2014 | Solène Savourey; Guillaume Lefèvre; Jean-Claude Berthet; Thibault Cantat, Chemical Communication, 2014

A novel methodology is presented for the direct methylation of amines, using formic acid as a unique source of carbon and hydrogen. Based on ruthenium(ii) catalysts, the formation of the N–CH3 group proceeds via an efficient formylation/transfer hydrogenation pathway.

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Silver(I)-Catalyzed Annulation for the Regioselective Synthesis of N-Imino-[gamma]-Carbolinium Ylides from Hydrazones of Indole-3-Carbonyl Derivatives and Propargylic Alcohols

21-10-2014 | Zhuang-ping Zhan; Yu Zhu; Xin-Rui Shen; Hai-tao Tang; Min Lin, Organic & Biomolecular Chemistry, 2014

A regioselective efficient synthetic approach to N-imino-γ-carbolinium ylides via AgOTf-catalyzed iminoannulation has been developed. This transformation proceeds via a silver(I) triflate-catalyzed consecutive Friedel-Crafts reaction/N-C bond formation sequence between readily available indole ...

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Orthogonal Selectivity with Cinnamic Acids in 3- substituted Benzofuran Synthesis through C–H Olefination of Phenols

21-10-2014 | Soumitra Agasti; Upendra Sharma; Togati Naveen; Debabrata Maiti, Chemical Communication, 2014

A palladium catalyzed intermolecular annulation of cinnamic acids and phenols has been achieved for the selective synthesis of 3-substituted benzofurans. Isotope labeling, competition experiments, kinetic studies, and intermediate trapping have supported a sequence of C–C bond formation, ...

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Spontaneous formation of organic helical architectures through dynamic covalent chemistry

21-10-2014 | Wenfang Li; Zeyuan Dong; Junyan Zhu; Quan Luo; Junqiu Liu, Chemical Communication, 2014

The spontaneous formation of organic helical structures, accompanied with an amplification of chirality, by dynamic covalent bonds between achiral and chiral building blocks is reported.

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